Oximino cyclic hydrocarbons

ABSTRACT

A METHOD FOR MANUFACTURING OXIMINO CYCLIC HYDROCARBONS BY DEHYDROHALOGENATION OF OXIMINO HALO CYCLIC HYDROCARBONS AND NOVEL COMPOSITIONS OBTAINED THEREBY ARE DISCLOSED. OXIMINOCYCLODODECATRIENES ARE PREPARED BY THE DEHYDROHALOGENATION OF OXIMINOCHLOROCYCLODODECADIENE IN THE PRESENCE OF A BASIC DEHYDROHALOGENATING AGENT. THE ONE EMBODIMENT DEHYDROHALOGENATION IN THE PRESENCE OF AN ORGANIC AMINE YIELDS A PRODUCT HAVING A MELTING POINT OF ABOUT 165-166*C. IN ANOTHER EMBODIMENT, USING AN INORGANIC BASE SUCH AS POTASSIUM HYDROXIDE IN TERTIARY BUTANOL YIELDS A PRODUCT HAVING A MELTING POINT OF FROM ABOUT 80*-85*C. WHICH IS A STEREOISOMER. THE UNSATURATED OXIMES OBTAINED ARE HYDROGENATED UNDER MILD REACTION CONDITIONS TO YIELD A SATURATED OXIME WHICH IS SUBJECTED TO A BECKMANN REARRANGEMENT TO YIELD A LACTAM AND THE LACTAM CONVERTED TO A POLYAMIDE WHICH IS USED IN THE MANUFACTURE OF FIBERS, FILAMENTS, MOLDED ARTICLES SUCH AS CONTAINERS AND THE LIKE. THE OXIME IS HYDROLYZED IN THE PRESENCE OF AN ACCEPTER FOR THE HYDROXYL AMINE PRODUCED AS A BY-PRODUCT OF THE HYDROLYSIS OF GIVE EITHER A SATURATED OR UNSATURATED KETONE DEPENDING ON WHETHER A SATURATED OR UNSATURATED OXIME IS USED AS THE STARTING MATERIAL. BOTH THE SATURATED AND UNSATURATED KETONES ARE USEFUL AS FRAGRANCE MATERIALS.

3,751,468 OXIMINO CYCLIC HYDROCARBONS Jerome Robert Olechowski, Trenton,N.J., assignor to Cities Service Company, New York, N.Y. N Drawing.Filed Aug. 20, 1971, Ser. No. 175,780 Int. Cl. C07c 131/08 U.S. Cl.260566 A 1 Claim ABSTRACT OF THE DISCLOSURE A method for manufacturingoximino cyclic hydrocarbons by dehydrohalogenation of oximino halocyclic hydrocarbons and novel compositions obtained thereby aredisclosed.

Oximinocyclododecatrienes are prepared by the dehydrohalogenation ofoximinochlorocyclododecadiene in the presence of a basicdehydrohalogenating agent. In one embodiment dehydrohalogenation in thepresence of an organic amine yields a product having a melting point ofabout 165166 C. In another embodiment, using an inorganic base such aspotassium hydroxide in tertiary butanol yields a product having amelting point of from about 80 -85 C. which is a stereoisomer.

The unsaturated oximes obtained are hydrogenated under mild reactionconditions to yield a saturated oxime which is subjected to a Beckmannrearrangement to yield a lactam and the lactam converted to a polyamidewhich is used in the manufacture of fibers, filaments, molded articlessuch as containers and the like.

The crime is hydrolyzed in the presence of an acceptor for the hydroxylamine produced as a by-product of the hydrolysis to give either asaturated or unsaturated ketone depending on whether a saturated orunsaturated oxime is used as the starting material. Both the saturatedand unsaturated ketones are useful as fragrance materials.

The dehydrohalogenation of an organic compound is known in the artwhereby hydrogen halide is removed from the compound and an unsaturatedorganic compound is obtained. The reaction is conducted in the presenceof a dehydrohalogenating agent such as lithium chloride in thecombination with dimethylformamide.

The attempted dehydrohalogenation of oximinohalocyclododecadieneaccording to the prior art method in which lithium chloride anddimethylformamide are employed as the dehydrohalogenation agent wasunsuccessful for the production of an oximino cyclic hydrocarbon andresulted in the manufacture of a tar-like product which could not beidentified.

Because the dehydrohalogenation reaction was unsuccessful employinglithium chloride and dimethylformamide with theoximinohalocyclododecadiene, it appears that the production of oximinocyclic hydrocarbons from the corresponding oximino halo cyclichydrocarbons by dehydrohalogenation is not possible.

It has been discovered that organic amines or inorganic bases includingthe basic metals and metal oxides, lower alkoxides or hydroxides can beused to dehydrohalogenate oximino halo cyclic hydrocarbons to obtain thecorresponding oximino cyclic hydrocarbon.

In one embodiment, it has been discovered that an organic amine can beused to dehydrohalogenate oxirninohalocyclododecadiene to yieldoximinocyclododecatrienc having a melting point of about 165 166 C.

In another embodiment, employing an inorganic base as thedehydrohalogenation agent, oximinocyclododecatriene having a meltingpoint of about 80-85 C. is obtained.

The difference in melting points of the foregoingoximinocyclododecatrienes is due to the fact that two differentstereoisomers are formed. Since the specific stereo United States Patent0 M 3,751,468 Patented Aug. 7, 1973 configuration of each of theoximinocyclododecatrienes has not been precisely identified, thesecompounds are presently identified by their melting points.

The oximino halo cyclic hydrocarbons employed are based on cyclichydrocarbons containing up to about 12 ring carbon atoms and substitutedwith oximino and halo groups. The oximino halo substituted cyclichydrocarbons have up to about 2. residual carbon-to-carbon unsaturatedpositions such as carbon-to-carbon double bonds. The residualunsaturation is defined as those unsaturated posi tions remaining in thering after oximino and halo substitution. The preferred oxirnino halosubstituted cyclic hydrocarbons are those containing 12 ring carbonatoms and 2 carbonto-carbon unsaturated positions especiallycarbon-to-carbon double bonds. The preferred substituted cyclichydrocarbons are also free of substituents other than oximino or halogroups.

The dehydrohalogenation of the foregoing oximino halo cyclichydrocarbons results in the production of an oximino unsaturated cyclichydrocarbon containing up to about 12 ring carbon atoms. The oximinounsaturated cyclic hydrocarbons immediately obtained will therefore,always, have one unsaturated group more than the oximino halo cyclichydrocarbon employed as the starting material. Thus, for example, wherethe OXimino halo cyclic hydrocarbon contains two unsaturated positions,upon dehydrohalogenation an oximino unsaturated cyclic hydrocarbonhaving 3 unsaturated groups is obtained.

The oximino unsaturated cyclic hydrocarbons obtained according to thepresent method may be hydrogenated to form oximino saturated cyclichydrocarbons having up to about 12 ring carbon atoms.

Novel oximino compounds are obtained by employing the aforementionedamine base dehydrohalogenation and comprise theoximinocyclododecatrienes, especially l-oximino-2,5,9-cyclododecatriene(melting point about 165 166 C.).

By employing the previously described process in which an inorganic baseis used in the dehydrohalogenation of oximinohalocyclododecadienes novelcompounds comprising oximinocyclododecatrienes are obtained, especially1- oximino-Z,5,9-cyclododecatriene (melting point about -85 (3.).

Any primary, secondary or tertiary amine may be used in the process,such as the alkyl amines, aryl amines or alkyl aryl amines andheterocyclic amines known in the art where the alkyl groups preferablyare lower alkyl groups and the aryl groups preferably are selected froma member of a group consisting of phenyl, benzyl, tolyl and xylyl andnaphthyl groups. The preferred amines are tertiary amines thehydrohalide salt of which is insoluble in the solvent in which thedehydrohalogenation reaction is conducted especially lower alkyltertiary amines. Tertiary amines employed in this respect include by wayof example diethylbenzylamine, diethyl-naphthyl-amine,diethylphenylarnine, triethylamine, trimethylamine, tripropylamine,tributylarnine and the various isomers thereof pyridine, piperidine,dirnethylaniline and the like or any combination thereof, especially the2 or 3 component combinations thereof. These amines are known in the artand are described in more detail in the Encyclopedia of Chemistry andTechnology, Kirk-Othmer.

The inorganic base employed comprises a Group I-A metal or a compositionderived from a Group I-A metal where the Group I-A metals are lithium,sodium, potassium, rubidium and cesium. The inorganic base is also aGroup II-A metal or derived from a Group ILA metal comprising beryllium,magnesium, calcium, strontium or barium. The preferred Group I-A metalsare lithium, sodium or potassium, Whereas the preferred Group II-Ametals are calcium, strontium or barium. The most preferred Group I-Ametals are sodium and potassium and the most preferred Group II-A metalis calcium.

The derivatives of the Group I-A or II-A metals including the preferredand most preferred species described above are the oxides, hydroxides oralkoxides, especially the lower alkoxides of the Group LA and II-Ametals. The Group LA and II-A metals, hydroxides, oxides or alkoxidesare preferably used in solution, suspension or dispersion especially anorganic solvent, as is the case with employing potassium hydroxide in alower alkanol. The Group LA and II-A metals, oxides, alkoxides orhydroxides, accordingly are preferably used in an organic solvent, suchas a lower alkanol, where the alkanol has up to about 4 carbon atoms aswell as the isomers thereof. Any combination of solvents, especially thetwo or three component combinations or azeotropic combinations areemployed.

The solvents should be inert towards the reactants by which it isintended that any solvent may be employed which is empirically observedto dissolve, suspend or disperse the reactants and which does not enterinto and/ or does not adversely affect the process.

When employing the aforementioned organic amine in the process, asolvent is selected that will not dissolve the by-product aminehydrochloride.

The addition of a nitrosyl halide to an unsaturated cyclic hydrocarbonfor obtaining the oximino cyclic 'halo hydrocarbons disclosed herein isgenerally conducted in the presence of a solvent such as acetic acid orany of the 1 to about 3 carbon atom aliphatic acids or mixtures thereof,the 1 to about 5 carbon atom aliphatic alcohols or mixtures thereof,esters of the said acids and said alcohols, mixtures of such esters,acetonitrile and aromatic solvents, such as for example, benzene,toluene and xylene, as well as aliphatic ethers having up to about atotal of 8 carbon atoms. Any combination of these solvents may be usedespecially the two or three component combinations or the azeotropiccombinations.

The oximino halocyclic hydrocarbon is obtained by the addition of anitrosyl halide, such as nitrosyl chloride or nitrosyl bromide to acyclic hydrocarbon having up to about 12. ring carbon atoms andcontaining up to about 3 unsaturated groups where the unsaturationcomprises at least one carbon-to-carbon double bond and preferably up toabout 3 carbon-to-carbon double bonds. The cyclic hydrocarbon ispreferably free from any other substituents. The resulting oximino halocyclic hydrocarbon will contain 1 less unsaturated group than thestarting cyclic hydrocarbon due to addition of the nitrosyl halide atthe unsaturated position of the cyclic hydrocarbon.

The halo and halide compositions referred to throughout thespecification and claims are intended to be those derived from thehalogens, chlorine, bromine and iodine, or any combination thereof. Thepreferred halogen is chlorine because the corresponding chloro andchloride compositions employed or obtained according to the presentinvention are either readily available or readily made, such as forexample, in the use of oximinochlorocyclododecadienes for the productionof oximinocyclododecatrienes.

Time, temperature and pressure conditions for conducting the reactionare not critical. The temperature generally should be sufiiciently highso that the reactants are readily suspended, dissolved or dispersed inthe solvent. For example, the dehydrohalogenation reaction can beconducted in a reaction vessel immersed in an ice bath. Temperaturesfrom about 10 to about 50 C. and pressures from about 0.5 atmosphere toabout 5 atmospheres may be employed. The pressure may be atmosphericwhich is intended to include any fluctuations in atmospheric pressuredue to a change in natural conditions. Higher or lower pressures may beemployed and are dictated to some extent by the volatility of thesolvent at the temperatures used for conducting the reaction. Thereaction is conducted for a period of time sufficient to obtain ameasurable yield of product.

The following examples are illustrative.

EXAMPLE 1 The following example illustrates the preparation of anoximino halo cyclic hydrocarbon and the dehydrohalogenation thereof bymeans of an organic amine.

A composition comprising 1-oximino-2-chlorocyclododeca-5,9-diene isprepared by the quantitative addition of nitrosyl chloride to1,5,9-cyclododecatriene in a solvent comprising acetic acid.

The 1-oximino-2-chlorocyclododeca-5,9-diene obtained (23.7 grams, 0.1mol) is then suspended in either a diethyl ether or benzene solvent towhich 13.0 grams (0.1 mol) of triethylamine is added to obtain a mixturewhich is stirred for several hours at room temperature and then cooledin an ice bath. Triethylamine hydrochloride is obtained as a by-productof the dehydrohalogenation reaction and is removed by filtration becauseit is insoluble in ether or benzene. A yield of triethylaminehydrochloride is obtained indicating a quantitative conversion of1-oximino-2-chlorocyclododeca-5,9-diene toloximino-2,5,9-cyclodecatriene the latter being recovered as a heavyviscous oil upon removal of the solvent by vacuum evaporation. The heavyviscous oil is then triturated with ethanol to give a white crystallinesolid having a melting point of -166 C. Infrared analysis shows strongabsorption for the oxime hydroxyl group as well as a strong band at 915cm.- for the =NO stretch, typical of oximes. The N.M.R. is alsoconsistent with the proposed structure.

Calculated for C H NO (percent): C, 75.39; H, 8.90; N, 7.33. Found(percent): C, 75.08, 74.92; H, 8.87, 8.94; N, 7.18, 7.13.

EXAMPLE 2 The following example describes the dehydrohalogenation of anoximinohalocyclododecadiene employing an inorganic base catalyst wherebythe stronger basicity of the catalyst results in the stereoisomerizationof the oximinocyclododecatriene to a stereo isomeric compound having amelting point of about 80-85 C.

The 1-oximino-2-chlorocyclododeca-5,9-diene prepared according to themethod of Example 1 is dehydrohalogenated with potassium hydroxide intertiary butyl alcohol in substantially the same manner as Example 1 anda stereoisomeric 1-oximino-2,5,9-cyclododecatriene having a meltingpoint of 80-85 C. is obtained. Infrared analysis shows no evidence fornitroso or nitroso chloro compounds. Strong absorption for oxime andalso for olefinic double bonds is obtained by infrared analysis. TheN.M.R. is consistent for the structure.

Calculated for C H NO (percent): C, 75.39; H, 8.90; N, 7.33. Found(percent): C, 74.93, 74.88; H, 8.89, 8.88; N, 6.85.

EXAMPLE 3 The following example illustrates a method for the productionof l-oximino-l-cyclododecane by the dehydrohalogenation ofoximinochlorocyclododecane.

Cyclododecene is reacted with nitrosyl chloride in acetic acid in orderto obtain 1-oximino-2-chlorocyclododecane.

The 1-oxirnino-2-chlorocyclododecane is then dehydrohalogenated insubstantially the same way as employed in the dehydroh-alogenationmethod of Example 1. The product obtained is 1-oximino-2-cyclododecene.

EXAMPLE 4 The following example illustrates that lithium chloride indimethylformamide does not function as a dehydrohalogenation agent for1-oximino-2-chlorocyclododeca- 5,9-diene.

The method of Example 1 is substantially repeated, however, lithiumchloride in dimethyl formamide is employed as a replacement for thetriethylamine and a dark colored tar-like material which could not beidentified is obtained.

The oximino unsaturated cyclic hydrocarbons obtained according to theinvention containing at least one carbonto-carbon double bond arehydrogenated to give the oximino hydrogenated or saturated cyclichydrocarbons. Hydrogenation is conducted under mild conditions to avoidreduction of the oximino group. Raney nickel and hydrogen at a pressurefrom about 60 to about 100 p.s.i.g. at about 20 C. is employed for asutficient length of time to hydrogenate any residual carbon-to-carbondouble bonds in the compound and to avoid reduction of the oximinogroup. In the case of l-oximino-2,5,9-cyclododecatriene, theoximinocyclododecane obtained by hydrogenation is converted by means ofa Beckmann rearrangement employing sulfuric acid as a catalyst to obtainthe lactam which, in turn, is heated to form a polyarnide or nylonpolymer which is used for the preparation of monofilaments, fibers andmolded articles such as containers and the like. The monofilaments andfibers are employed in the manufacture of woven, non-woven and knitfabrics.

The oximino saturated hydrocarbon and the oximino unsaturatedhydrocarbon, including the 1-oximino-2,5,9- cyclododecatriene, and1-oXimino2-cyclododecene is hydrolyzed by hydrogen chloride and water inthe presence of an acceptor for the hydroxylamine by-product of thehydrolysis in order to obtain the corresponding saturated andunsaturated ketones cyclododecanone-l-cyclododecene-2-one and2,5,9-cyclododecatrienel-one all of which are pleasant-smellingcompounds which are used as fragrance materials. The saturated ketone,cyclododecanone, is oxidized to dodecanoic acid by oxidation with air ornitric acid and the like and is used in the manufacture of polyestersbased on the condensation of equimolar amounts of phthalic acid, maleicacid and cyclododecanoic acid and a stoichiometric amount of propyleneglycol.

The polyester obtained, in turn, is cross-linked with about 30 weightpercent styrene in the presence of a benzoyl peroxide catalyst incombination with glass fibers in order to obtain a glass reinforcedpolyester composition.

When all the foregoing equivalent reaction conditions, and reactantswhich are described are employed, the same general results are obtainedas noted herein. Several of the equivalent conditions and reactants havebeen described broadly by reference to a range of equivalents by whichit is intended that such ranges are to include the specific reactants orvalues within a group of reactants or between the upper and the lowerlimits of such range of conditions, as well as narrower ranges orsmaller groups of reactants within the broad range of conditions andreactants disclosed. Thus, for example, the temperature for conductingthe dehydrohalogenation is about 20 C.; however, temperatures from about10 to about 40 C. may be employed and any specific value, for example,10 C., 40 C., 20 C., 15 C. or 12 C. falling within this broad range isalso intended as well as a narrower range within this broad range, suchas for example, 10 to about 15 C.

Furthermore, where the hydrocarbon, for example, has been describedpreferably as one containing up to about 12 ring carbon atoms, it isintended to include those hydrocarbons which can be described by anarrower range, such as hydrocarbons having from about 6 to about 12 orabout 8 to about 12 ring carbon atoms and so forth for the other rangesused to define the equivalents of the invention. The various conditionsand reactants described as being suitable for the present invention areused in any combination with one another and substantially the sameresults are obtained as disclosed herein.

Although the invention has been described by reference to certainembodiments, it is not intended that the novel compositions of matterand process be limited thereby but that certain modifications areintended to be included within the broad spirit and scope of theforegoing disclosure and the following claim.

What is claimed is:

1. l-oximino-2,5,9cyclododecatriene having a melting point of about l166C.

References Cited UNITED STATES PATENTS 2,394,430 2/1943 Crowder et a1.260-566 A 2,890,248 6/1959 Craig 260-566 A 3,303,217 2/1967 Genas et a1260-566 A Patai: The Chemistry of the Carbonyl Group, pp. 608-09 (1966).

LEON ZITVER, Primary Examiner G. A. SCHWARTZ, Assistant Examiner US. Cl.X.R. 2605 86 A

